EP0189836B1 - Basic azo dyes - Google Patents

Basic azo dyes Download PDF

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Publication number
EP0189836B1
EP0189836B1 EP86100832A EP86100832A EP0189836B1 EP 0189836 B1 EP0189836 B1 EP 0189836B1 EP 86100832 A EP86100832 A EP 86100832A EP 86100832 A EP86100832 A EP 86100832A EP 0189836 B1 EP0189836 B1 EP 0189836B1
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Prior art keywords
alkyl
hydrogen
oder
nhc
phenyl
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German (de)
French (fr)
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EP0189836A1 (en
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Horst Dr. Colberg
Erwin Dr. Hahn
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B44/00—Azo dyes containing onium groups
    • C09B44/02—Azo dyes containing onium groups containing ammonium groups not directly attached to an azo group

Definitions

  • DE-A-2 050 246 discloses cationic azo dyes whose diazo component is derived from special aniline derivatives which have an alkoxycarbonyl radical, the alkyl group still having a substituted ammonium radical.
  • R z. B preferred: C 2 H 4 or CH 2 CH (CH 3 ).
  • Alkyl radicals R 1 and R 2 generally have 1 to 14 carbon atoms and can be, for example, by N-cycloalkylamino, N, N-di-C 1 - to C 5 -alkylamino, hydroxy or C 1 - to C 8 -alkoxy be substituted. Also worth mentioning are allyl, methallyl or C 5 - to C 8 -cycloalkyl.
  • R 1 and R 2 together with the nitrogen can form, for example, the residues of the following heterocycles:
  • Pyrrolidine, piperidine, morpholine, piperazine, which on the nitrogen through methyl, ethyl, n- and i-propyl, n-, i-, sec-butyl, 2-hydroxyethyl, 2-aminoethyl, 2- or 3-hydroxypropyl, 2nd - Or 3-aminopropyl may be substituted, imidazole, which may be substituted in the 2- and / or 4-position by methyl, ethyl, propyl or butyl or N-3- (C 1 - to C 12 ) -alkyl or vinyl -imidazole, which can still be substituted in the 2- and / or 4-position by methyl, ethyl, propyl or butyl.
  • R 1 and R 2 are e.g. B .:
  • Preferred heterocyclic radicals are for example those of:
  • Morpholine piperidine, 4-methylpiperazine, 4-ethylpiperazine, 4-hydroxyethylpiperazine, 4- (2'-aminoethyl) piperazine, imidazole, 2-methylimidazole or 4-methylimidazole.
  • the rest can also be a group of formula be.
  • R 3 come z.
  • C 1 - to C 12 -alkyl or C 2 - to C 4 -hydroxyalkyl such as methyl, ethyl, n- or i-propyl, n- or i-butyl, n- or i-amyl, n- or i- Hexal, octyl, 2-ethylhexyl, decyl, dodecyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, hydroxybutyl, benzyl, CH 2 CH 2 (OH) CH 2 CI or CH 2 CH (OH) CH 2 0H.
  • R 3 is preferably C 1 -C 4 -alkyl, C 2 -C 4 -hydroxyalkyl or benzyl.
  • Methyl, ethyl and C 2 - or C 3 -hydroxyalkyl are particularly preferred for R3.
  • radicals carrying R 6 and R 7 are phenylene radicals of the formula II
  • the radicals of the formula II are in particular the 1,4 - phenylene radicals which are monosubstituted or disubstituted by methyl, methoxy, ethoxy or acylamino, acylamino, for example for NHCOCH 3 , NHCOC 2 H 5 , NHCOC 6 H 5 , NHCONH 2 , NHCON (CH 3 ) 2 or NHCONHC 6 H 5 .
  • NHCOCH 3 or NHCONHC 6 H 5 and the combination CH 3 / OCH 3 are particularly preferred.
  • R 8 are, for example, optionally chlorine, bromine, cyano, hydroxyl, C 1 -C 4 -alkoxy, C i -C 4 -alkoxycarbonyl, C 1 -C 4 -alkyl mercapto, phenoxy, sulfophenoxy, phenylmercapto, Amino, N-mono- or N, N-di-C 1 to C 4 alkylamino, phenylamino, sulfophenylamino, C 1 to C 4 alkanoylamino or sulfoethylamino substituted C 1 to C 4 alkyl, vinyl, cyclohexyl, optionally by fluorine, chlorine, bromine, hydroxy, Ci to C 4 alkoxy, ⁇ -C 1 to C 4 alkanoyloxyethoxy, ⁇ -cyanoethoxy, ⁇ -carboxylethyloxy, ⁇ -C 1 to C 4 -alkoxycarbony
  • R 8 radicals are preferably C 1 -C 4 -alkyl, ⁇ -carboxymethyl or optionally by chlorine, bromine, methyl, ethyl, C 1 -C 4 -alkoxy, ⁇ -cyanoethoxy, ⁇ -carboxylethoxy, phenoxy, sulfophenoxy, C 1 - to C 4 -alkanoylamino, phenylamino, sulfophenylamino or sulfoethylamino substituted phenyl.
  • R 9 and R 10 are, for example, C 1 -C 8 -alkyl radicals which are still interrupted by oxygen and by Hydroxy, carboxy, cyan, chlorine, bromine, phenyl, C 1 - to C 8 -alkoxy, C 1 - to C 4 -alkanoyloxy, C 1 - to C 4 -alkoxycarbonyl, C 1 - to C 4 -alkanoylamino, acetyl, C 1 to C 4 alkylaminocarbonyloxy, arylaminocarbonyloxy, C 1 to C 4 alkoxycarbonyloxy or phenoxycarbonyloxy may be substituted, allyl, methallyl, propargyl, cyclohexyl, phenyl-C 1 to C 5 -alkyl or optionally by fluorine, chlorine, Bromine, C 1 - to C 4 -alkoxycarbonyl, nitro or C 1 - to C 4 -alkanoylamino substitute
  • individual radicals R 9 and R 10 are, for example: hydrogen, methyl, ethyl, propyl, butyl, ⁇ -hydroxyethyl, ⁇ -methoxyethyl, y-methoxypropyl, ⁇ -cyanoethyl, ⁇ -carbomethoxyethyl, ⁇ -carboethoxyethyl, ⁇ - Acetoxyethyl, ⁇ -ethoxycarbonylethyl, y-acetylaminopropyt, phenoxycarbonyloxyethyl, phenylaminocarbonyloxyethyl, butylaminocarbonyloxyethyl, benzyl, ⁇ -phenethyl, phenyl, sulfophenyl, disulfophenyl, acetylaminophenyl, carboxyphenyl, cyanphenyl, chlorophenyl or sulfeth
  • R 9 and R 10 together with the nitrogen are, for example, oligomethyleneimino optionally interrupted by 0, N or S, such as, for example, pyrrolidino, piperidino, morpholino, piperazino, ⁇ -methylpiperazino, hexamethyleneimino or thiomorpholino-S-dioxide.
  • R 9 and R 10 independently of one another, preference is given to C 1 - to C 8 -alkyl, by hydroxy, carboxy, hydroxysulfonyl, cyano, phenyl, C 1 - to C 8 -alkoxy, phenoxy, C 1 - to C 4 -alkanoyloxy, C 1 - to C 4 -alkoxycarbonyl, C 1 - to C 4 -alkanoylamino or C 1 - to C 4 -alkoxycarbonyloxy-substituted C 2 - to C B -alkyl, allyl, phenyl-C 1 - to C 5 -alkyl or optionally phenyl substituted by chlorine, bromine, C 1 - to C 4 -alkyl, C 1 - to C 4 -alkoxy, cyan or carbamoyl and for (NR 9 R 10 ) pyrrolidino, piperidino, piperazino or morpholino.
  • Anions A ⁇ are z.
  • Amino compounds of the formulas can be used to prepare the compounds of the formulas Ia and Ib and diazotize and with the coupling component of the formula implement.
  • the compounds of the formulas Ia and Ib are suitable for dyeing acid-modified fibers such as polyacrylonitrile or polyesters, leather and in particular paper.
  • paper can also be printed with printing inks that contain aqueous acidic solutions from la and ib.
  • the bases or salts with longer-chain carboxylic or sulfonic acids such as oleic acid or dodecylbenzenesulfonic acid, they also come, for. B. for ballpoint pen pastes, solvent dyes or non-aqueous printing inks.
  • the dyes are also readily soluble in water and organic solvents, making them suitable for the production of liquid concentrates.
  • the dye can be dissolved with glacial acetic acid and water to a liquid setting. It colors paper stock intensely blue in shade no. 13, Color Index Hue Indication Chart. The wastewater is colorless. The colored paper can be bleached with hypochlorite. The fastness to bleeding against aqueous soda solution and water is excellent even in deep tones, and very good against aqueous acetic acid.
  • dyes can be produced from the corresponding halogenated or sulfochlorinated derivatives of isatoic anhydride, which dye paper blue.
  • Diazo component prepared according to Example 1 is distilled. 21 parts in 100 parts of toluene are added dropwise at 60 ° C. with 13 parts of dimethyl sulfate. The mixture is stirred for an hour at this temperature, cooled to room temperature and the precipitate is filtered off with suction. After drying, the diazotization equivalent is 355 g / val (theory 334 g / val). The connection corresponds to the formula
  • Example 2 After diazotization and coupling as in Example 1, the mixture is made alkaline with sodium hydroxide solution, the aqueous phase is decanted from the greasy dye and dissolved in aqueous glacial acetic acid.
  • a suspension of 50 parts of bleached sulfate pulp of about 30 ° SR in 2000 parts of water at pH 7 are 2 parts of a 10 percent.
  • acetic acid solution of the dye from Example 1 added.
  • the mixture is stirred for 15 minutes at 20 to 25 ° C and then diluted to 0.2% solids content with water.
  • paper sheets are produced on a laboratory sheet former and the sheets are dried at 10 ° C. for 5 minutes. Blue colored leaves are obtained.
  • the waste water is colorless, the bleeding fastness against Water and aqueous soda solution excellent, good against acetic acid.
  • An absorbent paper web made from unsized paper is drawn at 40-50 ° C. through a dye solution which is composed of 0.5 part of dye from Example 1, 0.5 part of starch, 3 parts of acetic acid and 96 parts of water. The excess dye solution is pressed between two rollers. The dried paper web is colored blue.
  • the dyes from the other examples can also be used analogously.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Polymerization Catalysts (AREA)
  • Coloring (AREA)

Description

Aus der DE-A-2 050 246 sind kationische Azofarbstoffe bekannt, deren Diazokomponente sich von speziellen Anilinderivaten ableitet, die einen Alkoxycarbonylrest aufweisen, wobei die Alkylgruppe noch einen substituierten Ammoniumrest besitzt.DE-A-2 050 246 discloses cationic azo dyes whose diazo component is derived from special aniline derivatives which have an alkoxycarbonyl radical, the alkyl group still having a substituted ammonium radical.

Es wurden nun neue Verbindungen der Formeln

Figure imgb0001
und
Figure imgb0002
gefunden, in denen

  • Y Wasserstoff, Chlor, Brom oder Nitro,
  • R gegebenenfalls durch Sauerstoff oder
    Figure imgb0003
    unterbrochenes Alkylen,
    Figure imgb0004
  • m die Zahlen 0 oder 1,
  • R1 und R2 unabhängig voneinander Wasserstoff, gegebenenfalls substituiertes Alkyl, Alkenyl, Cycloalkyl, Aralkyl oder Aryl oder
  • R1 und R2 zusammen mit dem Stickstoff einen Heterocyclus,
  • R3 Wasserstoff oder gegebenenfalls substituiertes Alkyl,
  • R6 und R7 unabhängig voneinander Wasserstoff, gegebenenfalls substituiertes Alkyl, Alkoxy oder Acylamino,
  • RB Wasserstoff, Acetyl, Benzoyl oder einen aliphatischen, cycloaliphatischen, aromatischen oder heterocyclischen Rest und
  • R9 und R10 unabhängig voneinander Wasserstoff, gegebenenfalls substituiertes Alkyl oder Cycloalkyl oder zusammen mit dem Stickstoff einen Heterocyclus und
  • A⊖ ein Anion bedeuten, wobei
  • R5 für Wasserstoff oder C1- bis C4-Alkyl steht und der Rest
    Figure imgb0005
  • auch für einen 1-Pyridylrest stehen kann.
Now there were new connections of the formulas
Figure imgb0001
 and
Figure imgb0002
 found in which
  • Y is hydrogen, chlorine, bromine or nitro,
  • R optionally by oxygen or
    Figure imgb0003
     interrupted alkylene,
    Figure imgb0004
  • m the numbers 0 or 1,
  • R 1 and R 2 are independently hydrogen, optionally substituted alkyl, alkenyl, cycloalkyl, aralkyl or aryl or
  • R 1 and R 2 together with the nitrogen form a heterocycle,
  • R 3 is hydrogen or optionally substituted alkyl,
  • R 6 and R 7 independently of one another are hydrogen, optionally substituted alkyl, alkoxy or acylamino,
  • R B is hydrogen, acetyl, benzoyl or an aliphatic, cycloaliphatic, aromatic or heterocyclic radical and
  • R 9 and R 10 independently of one another hydrogen, optionally substituted alkyl or cycloalkyl or together with the nitrogen a heterocycle and
  • A⊖ is an anion, where
  • R 5 represents hydrogen or C 1 to C 4 alkyl and the rest
    Figure imgb0005
  • can also represent a 1-pyridyl radical.

Gegebenenfalls substituierte Alkylenreste R haben z.B. 2 bis 10 C-Atome, bevorzugt sind C2-oder C3-Reste.

  • Im einzelnen sind beispielsweise zu nennen:
    Figure imgb0006
  • C2H4OC2H4, C3H6C3H6, C3H6OC2H4OC3H6,
  • C3H6OC4H8OC3H6, C3H60C2H40C2H40C3H6,
  • C2H4NHC2H4, C2H4NHC3H6, C3H6NHC3H6,
  • C3H6NHC2H4NHC3H6, C3H6NHC6H12NHC3H6,
    Figure imgb0007
Optionally substituted alkylene radicals R have, for example, 2 to 10 C atoms, C 2 or C 3 radicals are preferred.
  • The following can be mentioned in detail, for example:
    Figure imgb0006
  • C 2 H 4 OC 2 H 4 , C 3 H 6 C 3 H 6 , C 3 H 6 OC 2 H 4 OC 3 H 6 ,
  • C 3 H 6 OC 4 H 8 OC 3 H 6 , C 3 H 6 0C 2 H 4 0C 2 H 4 0C 3 H 6 ,
  • C 2 H 4 NHC 2 H 4 , C 2 H 4 NHC 3 H 6 , C 3 H 6 NHC 3 H 6 ,
  • C 3 H 6 NHC 2 H 4 NHC 3 H 6 , C 3 H 6 NHC 6 H 12 NHC 3 H 6 ,
    Figure imgb0007

Für R sind z. B. bevorzugt: C2H4 oder CH2CH(CH3).For R z. B. preferred: C 2 H 4 or CH 2 CH (CH 3 ).

Alkylreste R1 und R2 haben in der Regel 1 bis 14 C-Atome und können z.B. durch N-Cycloalkylamino, N,N-Di-C1- bis -C5-alkylamino, Hydroxy oder C1- bis C8-Alkoxy substituiert sein. Ferner sind Allyl, Methallyl oder C5- bis C8-Cycloalkyl zu erwähnen.Alkyl radicals R 1 and R 2 generally have 1 to 14 carbon atoms and can be, for example, by N-cycloalkylamino, N, N-di-C 1 - to C 5 -alkylamino, hydroxy or C 1 - to C 8 -alkoxy be substituted. Also worth mentioning are allyl, methallyl or C 5 - to C 8 -cycloalkyl.

Im einzelnen seien beispielsweise neben den bereits aufgeführten folgende Reste genannt:In particular, the following radicals may be mentioned in addition to those already listed:

Methyl, Ethyl, n-Propyl, i-Propyl, n-Butyl, i-Butyl, n-Amyl, i-Amyl, n-Hexyl, i-Hexyl, Heptyl, Octyl, 2-Ethylhexyl, Decyl, Dodecyl, Tridecyl, Tetradecyl, 2-Hydroxyethyl, 2- oder 3-Hydroxypropyl, Hydroxybutyl, Cyclopentyl, Cyclohexyl oder Cyclooctyl, N,N-Dimethylaminoethyl, N,N-Diethylaminoethyl, N,N-Dipropylaminoethyl, N,N-Dibutyl- aminoethyl, 3-(N,N-Dimethylamino)-propyl, 3-(N,N-Diethylamino)-propyl, 3-(N,N-Dipropylami- no)-propyl oder 3-(N,N-Dibutylamino)-propyl, N-Cyclohexylaminoethyl, 3-(N-Cyclohexylamino)-propyl, 3-(N-Cyclooctylamino)-propyl, N-Methyl-N-cyclohexylaminoethyl, 3-(N-Methyl-N-cyclohexyl- amino)-propyl, Benzyl, Phenethyl, Phenyl oderTolyl.Methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, n-amyl, i-amyl, n-hexyl, i-hexyl, heptyl, octyl, 2-ethylhexyl, decyl, dodecyl, tridecyl, Tetradecyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, hydroxybutyl, cyclopentyl, cyclohexyl or cyclooctyl, N, N-dimethylaminoethyl, N, N-diethylaminoethyl, N, N-dipropylaminoethyl, N, N-dibutylaminoethyl, 3- ( N, N-dimethylamino) propyl, 3- (N, N-diethylamino) propyl, 3- (N, N-dipropylamino) propyl or 3- (N, N-dibutylamino) propyl, N-cyclohexylaminoethyl , 3- (N-cyclohexylamino) propyl, 3- (N-cyclooctylamino) propyl, N-methyl-N-cyclohexylaminoethyl, 3- (N-methyl-N-cyclohexylamino) propyl, benzyl, phenethyl, phenyl or Tolyl.

R1 und R2 können zusammen mit dem Stickstoff z.B. die Reste folgender Heterocyclen bilden:R 1 and R 2 together with the nitrogen can form, for example, the residues of the following heterocycles:

Pyrrolidin, Piperidin, Morpholin, Piperazin, das am Stickstoff durch Methyl, Ethyl, n- und i-Propyl, n-, i-, sec.-Butyl, 2-Hydroxyethyl, 2-Aminoethyl, 2-oder 3-Hydroxypropyl, 2- oder 3-Aminopropyl substituiert sein kann, Imidazol, das in 2- und/oder 4-Stellung durch Methyl, Ethyl, Propyl oder Butyl substituiert sein kann oder N-3-(C1- bis C12)-Alkyl-oder Vinyl-imidazol, das in 2- und/oder 4-Stellung noch durch Methyl, Ethyl, Propyl oder Butyl substituiert sein kann.Pyrrolidine, piperidine, morpholine, piperazine, which on the nitrogen through methyl, ethyl, n- and i-propyl, n-, i-, sec-butyl, 2-hydroxyethyl, 2-aminoethyl, 2- or 3-hydroxypropyl, 2nd - Or 3-aminopropyl may be substituted, imidazole, which may be substituted in the 2- and / or 4-position by methyl, ethyl, propyl or butyl or N-3- (C 1 - to C 12 ) -alkyl or vinyl -imidazole, which can still be substituted in the 2- and / or 4-position by methyl, ethyl, propyl or butyl.

Bevorzugte Reste R1 und R2 sind z. B.:Preferred radicals R 1 and R 2 are e.g. B .:

Methyl, Ethyl, n-Propyl, i-Propyl, C2- oder C3-Hydroxyalkyl oder Cyclohexyl.Methyl, ethyl, n-propyl, i-propyl, C 2 - or C 3 -hydroxyalkyl or cyclohexyl.

Bevorzugte heterocyclische Reste

Figure imgb0008
sind z.B. die von:Preferred heterocyclic radicals
Figure imgb0008
 are for example those of:

Morpholin, Piperidin, 4-Methylpiperazin, 4-Ethylpiperazin, 4-Hydroxyethylpiperazin, 4-(2'-Aminoethyl)-piperazin, Imidazol, 2-Methylimidazol oder 4-Methylimidazol.Morpholine, piperidine, 4-methylpiperazine, 4-ethylpiperazine, 4-hydroxyethylpiperazine, 4- (2'-aminoethyl) piperazine, imidazole, 2-methylimidazole or 4-methylimidazole.

Der Rest

Figure imgb0009
kann auch eine Gruppe der Formel
Figure imgb0010
sein.The rest
Figure imgb0009
 can also be a group of formula
Figure imgb0010
 be.

Für R3 kommen daneben z. B. C1- bis C12-Alkyl oder C2- bis C4-Hydroxyalkyl wie Methyl, Ethyl, n-oder i-Propyl, n- oder i-Butyl, n- oder i-Amyl, n-oder i-Hexal, Octyl, 2-Ethylhexyl, Decyl, Dodecyl, 2-Hydroxyethyl, 2- oder 3-Hydroxypropyl, Hydroxybutyl, Benzyl, CH2CH2(OH)CH2CI oder CH2CH(OH)CH20H in Betracht.For R 3 come z. B. C 1 - to C 12 -alkyl or C 2 - to C 4 -hydroxyalkyl such as methyl, ethyl, n- or i-propyl, n- or i-butyl, n- or i-amyl, n- or i- Hexal, octyl, 2-ethylhexyl, decyl, dodecyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, hydroxybutyl, benzyl, CH 2 CH 2 (OH) CH 2 CI or CH 2 CH (OH) CH 2 0H.

Vorzugsweise steht R3 für C1- bis C4-Alkyl, C2- bis C4-Hydroxyalkyl oder Benzyl.R 3 is preferably C 1 -C 4 -alkyl, C 2 -C 4 -hydroxyalkyl or benzyl.

Für R3 sind Methyl, Ethyl und C2- oder C3-Hydroxyalkyl besonders bevorzugt.Methyl, ethyl and C 2 - or C 3 -hydroxyalkyl are particularly preferred for R3.

Die R6 und R7 tragenden Reste sind Phenylenreste der Formel II

Figure imgb0011
The radicals carrying R 6 and R 7 are phenylene radicals of the formula II
Figure imgb0011

Reste der Formel II sind insbesondere die durch Methyl, Methoxy, Ethoxy oder Acylamino einfach oder zweifach substituierten 1,4-Phenylenreste, wobei Acylamino z.B. für NHCOCH3, NHCOC2H5, NHCOC6H5, NHCONH2, NHCON(CH3)2 oder NHCONHC6H5 steht. Besonders bevorzugt sind NHCOCH3 oder NHCONHC6H5 sowie die Kombination CH3/OCH3.The radicals of the formula II are in particular the 1,4 - phenylene radicals which are monosubstituted or disubstituted by methyl, methoxy, ethoxy or acylamino, acylamino, for example for NHCOCH 3 , NHCOC 2 H 5 , NHCOC 6 H 5 , NHCONH 2 , NHCON (CH 3 ) 2 or NHCONHC 6 H 5 . NHCOCH 3 or NHCONHC 6 H 5 and the combination CH 3 / OCH 3 are particularly preferred.

Reste R8 sind beispielsweise gegebenenfalls durch Chlor, Brom, Cyan, Hydroxy, C1- bis C4-Alkoxy, Ci- bis C4-Alkoxycarbonyl, C1- bis C4-Alkyl- mercapto, Phenoxy, Sulfophenoxy, Phenylmercapto, Amino, N-mono- oder N,N-di-C1- bis C4- alkylamino, Phenylamino, Sulfophenylamino, C1- bis C4-Alkanoylamino oder Sulfoethylamino substituiertes C1- bis C4-Alkyl, Vinyl, Cyclohexyl, gegebenenfalls durch Fluor, Chlor, Brom, Hydroxy, Ci- bis C4-Alkoxy, β-C1- bis C4 Alkanoyloxyethoxy, β-Cyanethoxy, β-Carboxylethyloxy, β-C1- bis C4-Aikoxycarbonylethoxy, Phenoxy, Sulfophenoxy, C1- bis C4-Alkylmercapto, Phenylmercapto, Amino, β-C1- bis C4-Alkanoylamino, Benzoylamino, C1- bis C4-Alkylamino oder -Dialkylamino, Phenylamino, Sulfophenylamino, C1- bis C4-Alkylsul- fonylamino oder Phenylsulfonylamino substituiertes Phenyl, Thienyl oder Thiazolyl.R 8 are, for example, optionally chlorine, bromine, cyano, hydroxyl, C 1 -C 4 -alkoxy, C i -C 4 -alkoxycarbonyl, C 1 -C 4 -alkyl mercapto, phenoxy, sulfophenoxy, phenylmercapto, Amino, N-mono- or N, N-di-C 1 to C 4 alkylamino, phenylamino, sulfophenylamino, C 1 to C 4 alkanoylamino or sulfoethylamino substituted C 1 to C 4 alkyl, vinyl, cyclohexyl, optionally by fluorine, chlorine, bromine, hydroxy, Ci to C 4 alkoxy, β-C 1 to C 4 alkanoyloxyethoxy, β-cyanoethoxy, β-carboxylethyloxy, β-C 1 to C 4 -alkoxycarbonylethoxy, phenoxy, sulfophenoxy , C 1 - to C 4 -alkylmercapto, phenylmercapto, amino, β-C 1 - to C 4 -alkanoylamino, benzoylamino, C 1 - to C 4 -alkylamino or -dialkylamino, phenylamino, sulfophenylamino, C 1 - to C 4 - Alkylsulfonylamino or phenylsulfonylamino substituted phenyl, thienyl or thiazolyl.

Einzelne Reste R8 sind z.B.:

  • CH3, C2H5, CH2CI, CH2CN, CH20H, CH2-CH2Cl,
  • CH2-CH2OH, CH2-CH2CN, CH2-COOCH3,
  • CH2COOC2H5, -CH20CH3, -CH2OC2H5, CH2SCH3,
  • CH2N(CH3)2, C6H5OCH2, C6H5, ClC6H4, BrC6H4,
  • FC6H4, Cl2C6H3, CH3C6H4, (CH3)2C6H3, CH3OC6H4,
  • C2H5OC6H4, NCC2H4OC6H4, CH3OOC·C2H4OC6H4,
  • H2NCOC2H4OC6H4, CH3COOC2H4OC6H4,
  • HOC2H40C6H4, HOC6H4, C6H5OC6H4, CH3SC6H4,
  • C6H5SC6H4, NC-C2H4SC6H4, CH3CONHC6H4,
  • C2H5CONHC6H4, H2N-C6H4, HOC2H4NHC6H4,
  • (C2H5)2NC6H4, CH3SO2NHC6H4, C6H5SO2NHC6H4,
  • C6H5NHC6H4,
    Figure imgb0012
Individual radicals R 8 are, for example:
  • CH 3 , C 2 H 5 , CH 2 CI, CH 2 CN, CH 2 0H, CH 2 -CH 2 Cl,
  • CH 2 -CH 2 OH, CH 2 -CH 2 CN, CH 2 -COOCH 3 ,
  • CH 2 COOC 2 H 5 , -CH 2 0CH 3 , -CH 2 OC 2 H 5 , CH 2 SCH 3 ,
  • CH 2 N (CH 3 ) 2 , C 6 H 5 OCH 2 , C 6 H 5 , ClC 6 H 4 , BrC 6 H 4 ,
  • FC 6 H 4 , Cl 2 C 6 H 3 , CH 3 C 6 H 4 , (CH 3 ) 2 C 6 H 3 , CH 3 OC 6 H 4 ,
  • C 2 H 5 OC 6 H 4 , NCC 2 H 4 OC 6 H 4 , CH 3 OOC · C 2 H 4 OC 6 H 4 ,
  • H 2 NCOC 2 H 4 OC 6 H 4 , CH 3 COOC 2 H 4 OC 6 H 4 ,
  • HOC 2 H 4 0C 6 H 4 , HOC 6 H 4 , C 6 H 5 OC 6 H 4 , CH 3 SC 6 H 4 ,
  • C 6 H 5 SC 6 H 4 , NC-C 2 H 4 SC 6 H 4 , CH 3 CONHC 6 H 4 ,
  • C 2 H 5 CONHC 6 H 4 , H 2 NC 6 H 4 , HOC 2 H 4 NHC 6 H 4 ,
  • (C 2 H 5 ) 2 NC 6 H 4 , CH 3 SO 2 NHC 6 H 4 , C 6 H 5 SO 2 NHC 6 H 4 ,
  • C 6 H 5 NHC 6 H 4 ,
    Figure imgb0012

Reste R8 sind bevorzugt C1- bis C4-Alkyl, β-Carboxymethyl oder gegebenenfalls durch Chlor, Brom, Methyl, Ethyl, C1- bis C4-Alkoxy, β-Cyanethoxy, β-Carboxylethoxy, Phenoxy, Sulfophenoxy, C1- bis C4-Alkanoylamino, Phenylamino, Sulfophenylamino oder Sulfoethylamino substituiertes Phenyl.R 8 radicals are preferably C 1 -C 4 -alkyl, β-carboxymethyl or optionally by chlorine, bromine, methyl, ethyl, C 1 -C 4 -alkoxy, β-cyanoethoxy, β-carboxylethoxy, phenoxy, sulfophenoxy, C 1 - to C 4 -alkanoylamino, phenylamino, sulfophenylamino or sulfoethylamino substituted phenyl.

Reste R9 und R10 sind z.B. C1- bis C8-Alkylreste, die noch durch Sauerstoff unterbrochen und durch Hydroxy, Carboxy, Cyan, Chlor, Brom, Phenyl, C1- bis C8-Alkoxy, C1- bis C4-Alkanoyloxy, C1- bis C4-Alkoxycarbonyl, C1- bis C4-Alkanoylamino, Acetyl, C1- bis C4-Alkylaminocarbonyloxy, Arylaminocarbonyloxy, C1- bis C4-Alkoxycarbonyloxy oder Phenoxycarbonyloxy substituiert sein können, Allyl, Methallyl, Propargyl, Cyclohexyl, Phenyl-C1- bis C5-alkyl oder gegebenenfalls durch Fluor, Chlor, Brom, C1- bis C4-Alkoxycarbonyl, Nitro oder C1- bis C4-Alkanoylamino substituiertes Phenyl.R 9 and R 10 are, for example, C 1 -C 8 -alkyl radicals which are still interrupted by oxygen and by Hydroxy, carboxy, cyan, chlorine, bromine, phenyl, C 1 - to C 8 -alkoxy, C 1 - to C 4 -alkanoyloxy, C 1 - to C 4 -alkoxycarbonyl, C 1 - to C 4 -alkanoylamino, acetyl, C 1 to C 4 alkylaminocarbonyloxy, arylaminocarbonyloxy, C 1 to C 4 alkoxycarbonyloxy or phenoxycarbonyloxy may be substituted, allyl, methallyl, propargyl, cyclohexyl, phenyl-C 1 to C 5 -alkyl or optionally by fluorine, chlorine, Bromine, C 1 - to C 4 -alkoxycarbonyl, nitro or C 1 - to C 4 -alkanoylamino substituted phenyl.

Einzelne Reste R9 und R10 sind neben den bereits genannten beispielsweise: Wasserstoff, Methyl, Ethyl, Propyl, Butyl, β-Fiydroxyethyl, β-Methoxyethyl, y-Methoxypropyl, β-Cyanethyl, β-Carbomethoxyethyl, β-Carboethoxyethyl, β-Acetoxyethyl, β-Ethoxycarbonylethyl, y-Acetylaminopropyt, Phenoxycarbonyloxyethyl, Phenylaminocarbonyloxyethyl, Butylaminocarbonyloxyethyl, Benzyl, β-Phenethyl, Phenyl, Sulfophenyl, Disulfophenyl, Acetylaminophenyl, Carboxyphenyl, Cyanphenyl, Chlorphenyl oder Sulfethyl.In addition to those already mentioned, individual radicals R 9 and R 10 are, for example: hydrogen, methyl, ethyl, propyl, butyl, β-hydroxyethyl, β-methoxyethyl, y-methoxypropyl, β-cyanoethyl, β-carbomethoxyethyl, β-carboethoxyethyl, β- Acetoxyethyl, β-ethoxycarbonylethyl, y-acetylaminopropyt, phenoxycarbonyloxyethyl, phenylaminocarbonyloxyethyl, butylaminocarbonyloxyethyl, benzyl, β-phenethyl, phenyl, sulfophenyl, disulfophenyl, acetylaminophenyl, carboxyphenyl, cyanphenyl, chlorophenyl or sulfethyl.

R9 und R10 zusammen mit dem Stickstoff sind z.B. gegebenenfalls durch 0, N oder S unterbrochenes Oligomethylenimino, wie z.B. Pyrrolidino, Piperidino, Morpholino, Piperazino, a-Methylpiperazino, Hexamethylenimino oder Thiomorpholino-S-dioxid.R 9 and R 10 together with the nitrogen are, for example, oligomethyleneimino optionally interrupted by 0, N or S, such as, for example, pyrrolidino, piperidino, morpholino, piperazino, α-methylpiperazino, hexamethyleneimino or thiomorpholino-S-dioxide.

Bevorzugt sind für R9 und R10 unabhängig voneinander C1- bis C8-Alkyl, durch Hydroxy, Carboxy, Hydroxysulfonyl, Cyan, Phenyl, C1- bis C8-Alkoxy, Phenoxy, C1- bis C4-Alkanoyloxy, C1- bis C4-Alkoxycarbonyl, C1- bis C4-Alkanoylamino oder C1- bis C4-Alkoxycarbonyloxy substituiertes C2- bis CB-Alkyl, Allyl, Phenyl-C1- bis C5-Alkyl oder gegebenenfalls durch Chlor, Brom, C1- bis C4-Alkyl, C1- bis C4-Alkoxy, Cyan oder Carbamoyl substituiertes Phenyl sowie für (NR9R10) Pyrrolidino, Piperidino, Piperazino oder Morpholino.For R 9 and R 10, independently of one another, preference is given to C 1 - to C 8 -alkyl, by hydroxy, carboxy, hydroxysulfonyl, cyano, phenyl, C 1 - to C 8 -alkoxy, phenoxy, C 1 - to C 4 -alkanoyloxy, C 1 - to C 4 -alkoxycarbonyl, C 1 - to C 4 -alkanoylamino or C 1 - to C 4 -alkoxycarbonyloxy-substituted C 2 - to C B -alkyl, allyl, phenyl-C 1 - to C 5 -alkyl or optionally phenyl substituted by chlorine, bromine, C 1 - to C 4 -alkyl, C 1 - to C 4 -alkoxy, cyan or carbamoyl and for (NR 9 R 10 ) pyrrolidino, piperidino, piperazino or morpholino.

Anionen A⊖ sind z. B.: Chlorid, Bromid, Hydrogensulfat, Sulfat, Nitrat, Phosphat, Hydrogenphosphat, Dihydrogenphosphat, Carbonat, Hydrogencarbonat, Tetrachlorozinkat, Aminosulfonat, Methylsulfonat, Methylsulfat, Ethylsulfat, Formiat, Acetat, Hydroxyacetat, Aminoacetat, Methoxyacetat, Propionat, Lactat, Maleinat, Malonat, Citrat, Benzoat, Phthalat, Benzolsulfonat, Toluolsulfonat, Oleat oder Dodecylbenzolsulfonat.Anions A⊖ are z. For example: chloride, bromide, hydrogen sulfate, sulfate, nitrate, phosphate, hydrogen phosphate, dihydrogen phosphate, carbonate, hydrogen carbonate, tetrachlorozincate, aminosulfonate, methyl sulfonate, methyl sulfate, ethyl sulfate, formate, acetate, hydroxyacetate, amino acetate, methoxyacetate, malateate, malateate, malateate, malionate , Citrate, benzoate, phthalate, benzenesulfonate, toluenesulfonate, oleate or dodecylbenzenesulfonate.

Zur Herstellung der Verbindungen der Formeln la und Ib kann man Aminoverbindungen der Formeln

Figure imgb0013
und
Figure imgb0014
diazotieren und mit der Kupplungskomponente der Formel
Figure imgb0015
umsetzen.Amino compounds of the formulas can be used to prepare the compounds of the formulas Ia and Ib
Figure imgb0013
 and
Figure imgb0014
 diazotize and with the coupling component of the formula
Figure imgb0015
 implement.

Einzelheiten der Herstellung können den Beispielen entnommen werden, in denen sich Angaben über Teile und Prozente, sofern nichts anders vermerkt, auf das Gewicht beziehen.Details of the production can be found in the examples, in which information on parts and percentages, unless stated otherwise, relate to the weight.

Die Verbindungen der Formeln la und Ib eignen sich zum Färben von sauer modifizierten Fasern wie Polyacrylnitril oder Polyestern, Leder und insbesondere Papier. Auch lässt sich insbesondere Papier mit Druckfarben bedrucken, die wässrige saure Lösungen von la und Ib enthalten. In Form der Basen oder Salze mit längerkettigen Carbon-oder Sulfonsäuren wie Ölsäure oder Dodecylbenzolsulfosäure kommen sie auch z. B. für Kugelschreiberpasten, Solventfarbstoffe oder nicht wässrige Druckfarben in Betracht. Mit entsprechenden Anionen sind die Farbstoffe auch leicht in Wasser und organischen Lösungsmitteln löslich, so dass sie sich zur Herstellung von flüssigen Konzentraten eignen.The compounds of the formulas Ia and Ib are suitable for dyeing acid-modified fibers such as polyacrylonitrile or polyesters, leather and in particular paper. In particular, paper can also be printed with printing inks that contain aqueous acidic solutions from la and ib. In the form of the bases or salts with longer-chain carboxylic or sulfonic acids such as oleic acid or dodecylbenzenesulfonic acid, they also come, for. B. for ballpoint pen pastes, solvent dyes or non-aqueous printing inks. With the appropriate anions, the dyes are also readily soluble in water and organic solvents, making them suitable for the production of liquid concentrates.

Von besonderer Bedeutung sind Verbindungen der Formeln (la) und (Ib), in denen bedeuten:

  • Y: Wasserstoff oder Nitro;
  • R: C2H4, C3H6, -CH(CH3)CH2 oder C4H8;
  • R1 und R2: H, CH3, C2H5, n-, i-C3H7, n-, i-, sec.-C4H9, C2H40CH3,
    Figure imgb0016
    Figure imgb0017
    Figure imgb0018
    oder Cyclohexyl;
  • R3: CH3, C2H5 oder C2H40H;
  • R6 und R7: H, CH3, OCH3, OC2H5.
  • R8: C1- bis C4-Alkyl, β-Carboxymethyl oder gegebenenfalls durch Chlor, Brom, Methyl, Ethyl, Cl- bis C4-Alkoxy, β-Cyanethoxy, β-Carboxylethoxy, Phenoxy, Sulfophenoxy, C1- bis C4-Alkanoylamino, Phenylamino, Sulfophenylamino oder Sulfoethylamino substituiertes Phenyl. Besonders bevorzugt ist Phenyl.
  • R9 und R10: C1- bis C8-alkyl, durch Hydroxy, Carboxy, Hydroxysulfonyl, Cyan, Phenyl, C1- bis C8-Alkoxy, Phenoxy, Cl- bis C4-Alkanoyloxy, C1- bis C4-Alkoxycarbonyl, Cl- bis C4-Alkanoylamino oder Cl- bis C4-Alkoxycarbonyloxy substituiertes C2- bis C8-Alkyl, Allyl, Phenyl-C1- bis C5-Alkyl oder gegebenenfalls durch Chlor, Brom, Cl- bis C4-Alkyl, Cl- bis C4-Alkoxy, Cyan oder Carbamoyl substituiertes Phenyl und NR9R10 gegebenenfalls durch 0 oder N unterbrochenes Oligomethylenimino. Besonders bevorzugt für R9 und R10 sind Wasserstoff, Phenyl, Methyl, Ethyl oder Propyl, sowie für NR9R10 Morpholino, Piperazino oder Piperidino.
Compounds of the formulas (la) and (Ib) in which:
  • Y: hydrogen or nitro;
  • R: C 2 H 4 , C 3 H 6 , -CH (CH 3 ) CH 2 or C 4 H 8 ;
  • R 1 and R 2 : H, CH 3 , C 2 H 5 , n-, iC 3 H 7 , n-, i-, sec.-C 4 H 9 , C 2 H 4 0CH 3 ,
    Figure imgb0016
    Figure imgb0017
    Figure imgb0018
     or cyclohexyl;
  • R 3 : CH 3 , C 2 H 5 or C 2 H 4 0H;
  • R 6 and R 7 : H, CH 3 , OCH 3 , OC 2 H 5 .
  • R 8 : C 1 - to C 4 -alkyl, β-carboxymethyl or optionally by chlorine, bromine, methyl, ethyl, C l - to C 4 -alkoxy, β-cyanoethoxy, β-carboxylethoxy, phenoxy, sulfophenoxy, C 1 - to C 4 -alkanoylamino, phenylamino, sulfophenylamino or sulfoethylamino substituted phenyl. Phenyl is particularly preferred.
  • R 9 and R 10 : C 1 - to C 8 -alkyl, by hydroxy, carboxy, hydroxysulfonyl, cyano, phenyl, C 1 - to C 8 -alkoxy, phenoxy, C 1 - to C 4 -alkanoyloxy, C 1 - bis C 4 alkoxycarbonyl, C 1 to C 4 alkanoylamino or C 1 to C 4 alkoxycarbonyloxy substituted C 2 to C 8 alkyl, allyl, phenyl C 1 to C 5 alkyl or optionally by chlorine, bromine , C 1 to C 4 alkyl, C 1 to C 4 alkoxy, cyano or carbamoyl substituted phenyl and NR 9 R 10 optionally interrupted by 0 or N oligomethyleneimino. Hydrogen, phenyl, methyl, ethyl or propyl are particularly preferred for R 9 and R 10 , and morpholino, piperazino or piperidino for NR 9 R 10 .

BeispieleExamples Beispiel 1example 1

208 Teile Anthranilsäure-2'-dimethylaminoethyl- ester werden mit 500 Teilen Eis angerührt. Unter Aussenkühlung werden 500 Teile konz. Salzsäure, dann unterhalb 5°C 300 Volumenteile 23-proz. wässrige Natriumnitritlösung zugegeben. Bei 10-15°C rührt man drei Stunden, zerstört danach überschüssiges Nitrit durch Zugabe von Amidosulfonsäure und tropft eine Lösung von 129 Teilen 1-Naphthylamin in 250 Teilen Eisessig zu. Man lässt über Nacht auf Raumtemperatur kommen, saugt ab und wäscht mit 20-proz. Kochsalzlösung. Der Filterkuchen wird mit 500 Teilen Eis und 200 Teilen konz. Salzsäure angerührt. 300 Volumenteile 23-proz. wässrige Natriumnitritlösung werden zugetropft, wobei der pH-Wert durch Salzsäurezugabe unter 1 gehalten wird. Man rührt eine Stunde bei Raumtemperatur nach, zerstört überschüssiges Nitrit und tropft dann eine Lösung von 250 Teilen 2-Diethylamino-4-phenyl-1,3-thiazol in 200 Teilen Eisessig zu. Durch Zugabe von Natriumacetat wird ein pH von ungefähr 4,5 eingestellt und zwei Stunden nachgerührt. Danach saugt man ab, wäscht mit 20-proz. wässriger Kochsalzlösung, rührt den Filterkuchen in Ammoniakwasser auf, saugt wieder ab und wäscht mit Wasser. Nach der Gefriertrocknung werden 1203 g der mit Salz verunreinigten Farbstoffs der Formel

Figure imgb0019
erhalten. Schmelzpunkt 75°C, λmax (50-proz. Essigsäure) = 584208 parts of 2'-dimethylaminoethyl anthranilic acid are mixed with 500 parts of ice. 500 parts of conc. Hydrochloric acid, then below 5 ° C 300 parts by volume 23 percent. aqueous sodium nitrite solution added. The mixture is stirred for three hours at 10-15 ° C., then excess nitrite is destroyed by adding amidosulfonic acid and a solution of 129 parts of 1-naphthylamine in 250 parts of glacial acetic acid is added dropwise. Allow to come to room temperature overnight, suction and wash with 20 percent. Saline. The filter cake is concentrated with 500 parts of ice and 200 parts. Stirred hydrochloric acid. 300 parts by volume 23 percent aqueous sodium nitrite solution are added dropwise, the pH being kept below 1 by adding hydrochloric acid. The mixture is stirred for one hour at room temperature, excess nitrite is destroyed and then a solution of 250 parts of 2-diethylamino-4-phenyl-1,3-thiazole in 200 parts of glacial acetic acid is added dropwise. A pH of about 4.5 is set by adding sodium acetate and stirring is continued for two hours. Then you suction, wash with 20 percent. aqueous saline solution, stir the filter cake in ammonia water, suction again and wash with water. After freeze-drying, 1203 g of the dye of the formula contaminated with salt
Figure imgb0019
 receive. Melting point 75 ° C, λmax (50 percent acetic acid) = 584

Der Farbstoff lässt sich mit Eisessig und Wasser zu einer Flüssigeinstellung auflösen. Er färbt Papierstoff intensiv blau im Farbton No. 13, Colour Index Hue Indication Chart. Das Abwasser istfarblos. Das gefärbte Papier lässt sich mit Hypochlorit bleichen. Die Ausbluteechtheit gegen wässrige Sodalösung und Wasser ist auch in tiefen Tönen hervorragend, die gegen wässrige Essigsäure sehr gut.The dye can be dissolved with glacial acetic acid and water to a liquid setting. It colors paper stock intensely blue in shade no. 13, Color Index Hue Indication Chart. The wastewater is colorless. The colored paper can be bleached with hypochlorite. The fastness to bleeding against aqueous soda solution and water is excellent even in deep tones, and very good against aqueous acetic acid.

Analog dem beschriebenen Verfahren lassen sich weitere Farbstoffe herstellen, die im Farbton und der Affinität zu Papierstoff weitgehend der obigen Verbindung entsprechen.

Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
 Analogous to the process described, other dyes can be produced which largely correspond to the above compound in terms of color and affinity for paper stock.
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025

Analog Beispiel 1 lassen sich aus den entsprechenden halogenierten bzw. sulfochlorierten Derivaten des Isatosäureanhydrids weitere Farbstoffe herstellen, die Papier blau färben.

Figure imgb0026
Figure imgb0027
 Analogously to Example 1, further dyes can be produced from the corresponding halogenated or sulfochlorinated derivatives of isatoic anhydride, which dye paper blue.
Figure imgb0026
Figure imgb0027

Beispiel 58Example 58

Herstellung der Diazokomponente: Nach Beispiel 1 hergestellte Diazokomponente wird destilliert. 21 Teile werden in 100 Teilen Toluol tropfenweise bei 60°C mit 13 Teilen Dimethylsulfat versetzt. Man rührt eine Stunde bei dieser Temperatur nach, kühlt auf Raumtemperatur und saugt den Niederschlag ab. Nach der Trocknung beträgt das Diazotierungsäquivalent 355 g/val (Theorie 334 g/ val). Die Verbindung entspricht der FormelPreparation of the diazo component: Diazo component prepared according to Example 1 is distilled. 21 parts in 100 parts of toluene are added dropwise at 60 ° C. with 13 parts of dimethyl sulfate. The mixture is stirred for an hour at this temperature, cooled to room temperature and the precipitate is filtered off with suction. After drying, the diazotization equivalent is 355 g / val (theory 334 g / val). The connection corresponds to the formula

Figure imgb0028
Figure imgb0028

Nach Diazotierung und Kupplung analog Beispiel 1 stellt man mit Natronlauge alkalisch, dekantiert die wässrige Phase vom schmierigen Farbstoff und löst in wässrigem Eisessig. Der Farbstoff färbt Papierstoff blau bei mässiger Abwasseranfärbung und entspricht nun der Formel

Figure imgb0029
After diazotization and coupling as in Example 1, the mixture is made alkaline with sodium hydroxide solution, the aqueous phase is decanted from the greasy dye and dissolved in aqueous glacial acetic acid. The dye dyes paper stock blue with moderate wastewater staining and now corresponds to the formula
Figure imgb0029

Beispiel 59Example 59

Einer Suspension von 50 Teilen gebleichtem Sulfatzellstoff von ca. 30° SR in 2000 Teilen Wasser bei pH 7 werden 2 Teile einer 10-proz. essigsauren Lösung des Farbstoffs aus Beispiel 1 zugegeben. Das Gemisch wird 15 Minuten bei 20 bis 25°C gerührt und dann mit Wasser auf 0,2% Feststoffgehalt verdünnt. Mit dieser Suspension werden auf einem Laborblattbildner Papierblätter hergestellt und die Blätter 5 Minuten bei 10°C getrocknet. Man erhält blau gefärbte Blätter. Das Abwasser ist farblos, die Ausblutechtheit gegen Wasser und wässrige Sodalösung hervorragend, gegen Essigsäure gut.A suspension of 50 parts of bleached sulfate pulp of about 30 ° SR in 2000 parts of water at pH 7 are 2 parts of a 10 percent. acetic acid solution of the dye from Example 1 added. The mixture is stirred for 15 minutes at 20 to 25 ° C and then diluted to 0.2% solids content with water. With this suspension, paper sheets are produced on a laboratory sheet former and the sheets are dried at 10 ° C. for 5 minutes. Blue colored leaves are obtained. The waste water is colorless, the bleeding fastness against Water and aqueous soda solution excellent, good against acetic acid.

Verwendung der Farbstoffe aus den anderen Beispielen erbringt ähnlich gute Färbeergebnisse.Use of the dyes from the other examples gives similarly good coloring results.

Beispiel 60Example 60

In eine gerührte Suspension aus 100 Teilen eines Gemisches von 70% gebleichtem Kiefernsulfatzellstoff und 30% gebleichtem Birkensulfatzellstoff mit ca. 30° SR im Gesamtstoff in 2000 Teilen Wasser werden 1,0 Teile des Vermahlungsproduktes aus 90% Farbstoff nach Beispiel 1 und 10% Amidosulfonsäure eingestreut und 10 Minuten verrührt. Nach Verdünnung mit Wasser auf 0,2% Feststoffgehalt werden auf einem Laborblattbildner Papierblätter hergestellt und die Blätter 5 Minuten bei 100°C getrocknet. Man erhält gleichmässig blau gefärbte Blätter mit hervorragender Ausblutechtheit gegen Wasser. Verwendung von Vermahlungsprodukten der Farbstoffe aus Beispiel 2-70 mit Amidosulfonsäure erbringt ähnlich gute Färbeergebnisse.In a stirred suspension of 100 parts of a mixture of 70% bleached pine sulfate pulp and 30% bleached birch sulfate pulp with approx. 30 ° SR in total in 2000 parts of water, 1.0 part of the ground product of 90% dye according to Example 1 and 10% amidosulfonic acid are sprinkled in and stirred for 10 minutes. After dilution with water to a solids content of 0.2%, paper sheets are produced on a laboratory sheet former and the sheets are dried at 100 ° C. for 5 minutes. You get uniform blue colored leaves with excellent bleeding resistance to water. Use of grinding products of the dyes from Example 2-70 with amidosulfonic acid produces similarly good dyeing results.

Beispiel 61Example 61

Eine saugfähige Papierbahn aus ungeleimten Papier wird bei 40-50°C durch eine Farbstofflösung gezogen, die sich zusammensetzt aus 0,5 Teilen Farbstoff aus Beispiel 1, 0,5 Teilen Stärke, 3 Teilen Essigsäure und 96 Teilen Wasser. Die überschüssige Farbstofflösung wird zwischen zwei Walzen abgepresst. Die getrocknete Papierbahn ist blau gefärbt.An absorbent paper web made from unsized paper is drawn at 40-50 ° C. through a dye solution which is composed of 0.5 part of dye from Example 1, 0.5 part of starch, 3 parts of acetic acid and 96 parts of water. The excess dye solution is pressed between two rollers. The dried paper web is colored blue.

Analog können auch die Farbstoffe aus den anderen Beispielen eingesetzt werden.The dyes from the other examples can also be used analogously.

Claims (2)

1. Compounds of the formulae
Figure imgb0035
and
Figure imgb0036
where Y is hydrogen, chlorine, bromine or nitro, R is alkylene which may or may not be interrupted by oxygen or
Figure imgb0037
or is
Figure imgb0038
m is 0 or 1,
R1 and R2 independently of one another are each hydrogen, unsubstituted or substituted alkyl, alkenyl, cycloalkyl, aralkyl or aryl, or R1 and R2 together with the nitrogen form a heterocyclic structure, R3 is hydrogen or unsubstituted or substituted alkyl, R6 and R7 independently of one another are each hydrogen, unsubstituted or substituted alkyl, alkoxy or acylamino, R8 is hydrogen, acetyl, benzoyl, or an aliphatic, cycloaliphatic, aromatic or heterocyclic radical, R9 and R10 independently of one another are each hydrogen, unsubstituted or substituted alkyl or cycloalkyl, or together with the nitrogen form a heterocyclic structure and A- is an anion, where R is hydrogen or C1-C4-alkyl and the radical
Figure imgb0039
may furthermore be 1-pyridyl.
2. Use of the compounds as claimed in claim 1 for dyeing paper.
EP86100832A 1985-01-26 1986-01-22 Basic azo dyes Expired EP0189836B1 (en)

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